Classifications

• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
  • A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
  • Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
  • Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture

Definitions

• the present invention relates to plant growth-regulating, in particular yield-increasing and gametocidal agents which contain a benzoylaminooxyacetic acid derivative as active ingredient. It also relates to the use of these agents and the active ingredients contained in them to regulate generative plant growth and the use for the production of male-sterile plants as a prerequisite for the production of hybrid seeds. The invention also relates to the new benzoylaminooxyacetic acid derivatives and their production processes.
• alkyl itself or alkyl as part of another substituent means, depending on the number of carbon atoms indicated, for example the following groups: methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl or tert-butyl.
• Alkenyl stands for example for vinyl, 1-propenyl, allyl, 1-butenyl, 2-butenyl, 3-butenyl etc. and also chains with several double bonds. Allyl is preferred.
• Alkynyl means, for example, 1-propynyl, propargyl, 1-butynyl, 2-butynyl, etc. Propargyl is preferred.
• Haloalkyl stands for a mono- to perhalogenated alkyl substituent, such as CHCl 2 , CH 2 Cl, CCl 3 , CF 3 , CH 2 CF 3 , CH 2 CH 2 Cl, etc.
• Halogen and fluorine, chlorine, bromine should be used here and below or iodine, preferably fluorine, chlorine or bromine.
• Haloalkenyl and haloalkynyl each represent an alkenyl or alkynyl group which is mono- or polysubstituted by halogen, chlorine and bromine, in particular chlorine, being preferred as halogen.
• a cation is understood to mean, for example, the inorganic cation of an element from the first to fourth main groups of the periodic table.
• Typical representatives are the alkali metals such as lithium, sodium, potassium or the alkaline earth metals such as magnesium, calcium, barium or elements such as aluminum or tin.
• This also means the cation of an element from the first to eighth subgroups, such as, for example, manganese, iron, nickel, copper, zinc or silver.
• Alkali and alkaline earth metal cations and the cations of the elements from the third and fourth period of the periodic table are preferred.
• the term cation also stands for organic Cations such as ammonium ions or for hydrazinium ions.
• ammonium ions are: NH 4 , NH (alkyl) 3 , NH 2 (alk y l) 2 and NH 3 (alkyl) such as NH (CH 3 ) 3 , NH (C 2 H 5 ) 3 , NH 2 ( CH 3) 2, NH 2 (C 3 H 7 -n) 2, NH 3 CH 3, NH 3 C 4 H 9 -n or quaternary ammonium ions such as tetraethyl, tetrapropyl -, tetrabutyl-, tetrapentyl-, tetrahexylammonium, Tetraheptyl -, tetraoctyl-, tetranonyl-, tetradecyl-, methyltributyl-, dimethyldi - butyl-, trimethylbutyl-, methyltrioctyl-, benzyltrimethyl-, benzyltrie
• Possible hydrazinium ions are unsubstituted and substituted hydrazinium compounds, such as NH 2 NH 3 + , NH 2 N (alkyl) + 3 , NH 2 NH (alkyl) + 2 , NH 2 NH 2 (alkyl) + etc.
• tetraalkylammonium ions such as N (CH 3 ) + 4 , N (C 2 H 5 ) + 4 , N (C 4 H 9-n ) 4 + , N (CH 3 ) 2 (C 2 H 5 ) + 2 , N (C 3 H 7 -n) + 4 , N (C 3 H 4 -i) + 4 , etc.
• formula I also includes the salts already mentioned, the amides, the esters and thioesters.
• the alcohols on which the esters or thioesters are based are: methanol, ethanol, n-propanol, i-propanol, n-butanol, phenol, anisole, 4-chlorophenol, 2,4-dichlorophenol, 3,4-dichlorophenol, 2,6 -Dichlorophenol, 3,4-dimethoxyphenol, ethylene glycol monomethyl ether, benzyl alcohol, 2,3-dichloroallyl alcohol, methoxymethanol, ethoxy methanol, ethylene glycol monoethyl ether, 2,2,2-trifluoroethanol, 2-chloroethanol, allyl alcohol, propargyl alcohol or methhalo alcohol, as well as zimlyl alcohol; of these alcohols.
• the compounds of formula I are oils, resins or predominantly solids which are stable at room temperature and which are distinguished by very valuable plant growth regulating, in particular yield-increasing and Characterize gametocidal properties. They can therefore preferably be used in the agricultural sector or related fields for the targeted influencing of crops.
• a preferred subgroup of active compounds of the formula 1 are the 2,6-dihalobenzoylaminooxyacetic acid derivatives of the sub-formula la and their salts, in which the substituents Hal independently of one another represent halogen and R 1 , R 2 , R 3 and R 4 have the meaning given under formula I in claim 1.
• R 1 , R 2 and R 3 are hydrogen and R 4 is hydroxyl or C 1 -C 4 -alkoxy, preferably methoxy or ethoxy.
• Preferred individual active ingredients are 2,6-dichlorobenzoylaminooxyacetic acid and its methyl ester.
• the active compounds of the formula I can be prepared by various methods.
• the compounds of the formula I are obtained by using a benzoylhydroxamic acid of the formula II wherein X 1 , X 2 and R 1 have the meaning given under formula I, in the presence of an acid-binding agent with an ⁇ -haloacetic acid derivative of the formula III wherein R 2 , R 3 and R 4 have the meaning given under formula I and Z 1 represents halogen, in particular chlorine or bromine, with elimination of hydrogen halide.
• Suitable solvents are, for example, alkanols, ethers and ethereal compounds such as diethyl ether, diisopropyl ether, t-butyl methyl ether, dimethoxyethane, dioxane, tetrahydrofuran, anisole; Ketones such as acetone, methyl ethyl ketone; Esters such as ethyl acetate, butyl acetate and mixtures of such solvents with one another. Mixtures with other inert solvents, e.g. with aromatic or aliphatic hydrocarbons can be used.
• Acid-binding agents include, in particular, tertiary amines such as trimethylamine, triethylamine, quinuclidine, 1,4-diazabicyclo (2,2,2) octane, 1,5-diazabicyclo (4,3,0) non-5-ene or 1,5-diazabicyclo (5,4,0) undec-7-ene.
• tertiary amines such as trimethylamine, triethylamine, quinuclidine, 1,4-diazabicyclo (2,2,2) octane, 1,5-diazabicyclo (4,3,0) non-5-ene or 1,5-diazabicyclo (5,4,0) undec-7-ene.
• inorganic bases such as hydrides such as sodium or calcium hydride, hydroxides such as sodium and potassium hydroxide, carbonates such as sodium and potassium carbonate or hydrogen carbonates such as potassium and sodium hydrogen carbonate can also be used.
• the reaction is advantageously carried out at elevated temperature, generally between 0 ° and 120 ° C., usually at the boiling point of the solvent or solvent mixture.
• the starting compounds of the formulas II and III are generally known and can be prepared by methods known per se.
• benzoylaminooxyacetic acid derivatives of the formula I in which R 4 is -OR 6 can be prepared by using an aminooxyacetic acid derivative of the formula IV or V wherein R, R 2 , R 3 and R 6 have the meaning given under formula I and Z 2 represents chlorine or bromine, in the presence of an acid-binding agent with a benzoyl halide of the formula VI implements in which X 1 and X 2 have the meaning given under formula I and Z 3 represents chlorine or bromine.
• Suitable acid-binding agents are, for example, alkali and alkaline earth metal hydroxides, carbonates, bicarbonates or oxides such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, sodium hydrogen carbonate, magnesium oxide or calcium oxide or organic bases such as e.g. Trimethylamine, diethylamine, triethylamine, piperidine, pyrrolidine, pyridine, quinoline or quinuclidine.
• the compounds of the formula I in which R 4 represents an ester or thioester group can also be prepared by using an aminooxyacetic acid derivative of the formula VII wherein R, R, R, R and Y have the meaning given under formula I, in the presence of a condensing agent, such as, for example, dicyclohexylcarbodiimide, with a benzoic acid of the formula (VIII) in which X 1 and X 2 have the meaning given under formula I.
• a condensing agent such as, for example, dicyclohexylcarbodiimide
• the acids, esters, thioesters or amides obtained can be converted into one another by generally known methods such as hydrolysis, transesterification, transamidation, esterification, amidation or by combinations of these process steps.
• ammonium and hydrazinium salts of formula I are by reaction of a free acid I with the corresponding amine or hydrazine accessible.
• Metal salts of the formula I are obtained, for example, by reacting the free acid I with a corresponding basic metal salt, for example a hydroxide, carbonate, alcoholate, etc.
• the new 2,6-dihalobenzoylaminooxyacetic acid derivatives of the formula Ia can also be prepared by the preparation processes mentioned. They are produced by the processes mentioned using the benzoic acid derivatives of the formulas IIa, VIa or VIIIa wherein the substituents HaI each independently represent halogen atoms, R 1 has the meaning given under formula I and Z 3 represents chlorine or bromine. These manufacturing methods form part of the present invention.
• the active compounds of the formula I or compositions which contain these active compounds are distinguished above all by the fact that they specifically intervene in the metabolism of the plants.
• This targeted intervention in the physiological processes of plant development makes the active ingredients of the formula I usable for various purposes, in particular for those which are associated with the increase in yield in useful plants, the easier harvesting and the labor savings in measures on plant crops.
• the application of growth regulators means that the active substances can cause one or more different effects on the plants. These various effects depend essentially on the time of application, i.e. on the physiological state of the seed or on the state of development of the plant, the type of application and in particular on the concentrations used. Such effects in turn differ depending on the type of plant.
• the application of compounds of the formula I now opens up the possibility of influencing the growth of plants in the desired manner.
• Plant growth regulating substances can be used, for example, to inhibit vegetative plant growth.
• Such inhibition of growth is of economic interest, among other things, for grasses, because it can e.g. the frequency of grass cuts in ornamental gardens, parks and sports facilities or on the side of the road can be reduced. It is also important to inhibit the growth of herbaceous and woody plants on the side of the road and in the vicinity of overhead lines or in general in areas in which heavy growth is undesirable.
• growth regulators it is also important to use growth regulators to inhibit the growth in length of cereals, because shortening the stalk increases the risk of the plants bending ("storing") before harvesting reduced or completely eliminated.
• growth regulators in cereals can cause stalk reinforcement, which also counteracts storage.
• An inhibition of vegetative growth allows a denser cultivation of the crop in many crop plants, so that an additional yield, based on the soil area, can be achieved.
• Another mechanism of increasing yield with growth inhibitors is based on the fact that the nutrients benefit the bloom and fruit formation to a greater extent, while vegetative growth is restricted.
• Growth regulators can often also be used to promote vegetative growth. This is of great benefit when the vegetative parts of the plant are harvested. A promotion of vegetative growth can also lead to a promotion of generative growth, so that e.g. more or bigger fruits come to training.
• increases in yield can also be achieved by intervening in plant metabolism without any changes in vegetative growth being noticeable.
• Growth regulators can also cause a change in the composition of the plants, so that a better quality of the harvested products is brought about. For example, it is possible to increase the sugar content in sugar beet, sugar cane, pineapple and citrus fruits or to increase the protein content in soybeans or cereals.
• Parthenocarpic fruits can develop under the influence of growth regulators.
• the gender of the flowers can also be influenced.
• Growth regulators can also have a positive impact on the production or outflow of phytochemicals.
• One example is the stimulation of latex flow in rubber trees.
• growth regulators can also be used to increase the lateral branching by chemically breaking the apical dominance. Interest in plant propagation. However, it is also possible to inhibit the growth of the side shoots, e.g. to prevent the formation of side shoots in tobacco plants after decapitation and thus to promote leaf growth.
• the number of leaves on plants can be controlled in such a way that defoliation of the plants is achieved at a desired point in time. Such defoliation is of interest in order to achieve mechanical harvesting e.g. for wine or cotton, to facilitate or to reduce perspiration at a time when the plant is to be transplanted.
• the use of growth regulators can prevent premature fruiting. However, it is also possible to promote fruit dropping, for example in the case of fruit, by chemical thinning to a certain extent. Growth regulators can also be used to reduce the force required to detach the fruit from crops at the time of harvesting, so that mechanical harvesting of the plants is made possible or manual harvesting is facilitated.
• growth regulators it is also possible to accelerate or delay the ripening of the crop before or after the harvest. This is particularly advantageous because it results in an optimal adaptation to the needs of the market leaves. Furthermore, growth regulators can improve fruit coloration in some cases. In addition, growth regulators can also be used to concentrate the maturity over time. This creates the prerequisites for complete mechanical or manual harvesting in a single operation, for example with tobacco, tomatoes or coffee.
• growth regulators can also influence the rest of the seeds or buds of the plants, i.e. the endogenous annual rhythm, so that the plants, e.g. Pineapples or ornamental plants in nurseries, germinate, sprout or bloom at a time when they are usually not ready to do so.
• Growth regulators can also be used to delay bud budding or seed germination, e.g. to avoid damage from late frosts in areas at risk of frost.
• a larger, better-developed root system can improve stress relief (dryness), improve the absorption of nutrients and thus increase yields.
• Growth regulators can also produce halophilia in crops. This creates the conditions for cultivating plants on saline soils.
• cover crops are used to inhibit excessive growth in tropical soil cover plants, the so-called cover crops.
• cover crops In tropical and subtropical monocultures, e.g. In palm plantations, cotton, maize fields, etc., in addition to the actual crop plants, land cover plants, in particular legume species, are often planted, which serve to maintain or increase the soil quality (prevention of drying out, supply of nitrogen) and to prevent erosion (erosion by wind and water) .
• the active compounds according to the invention the growth of these cover crops can now be controlled and the growth height of these ground covering plants can thus be kept at a low level, so that the healthy growth of the crop plants and the maintenance of a favorable soil quality is ensured.
• benzoylaminooxyacetic acid derivatives of the formula I or compositions which contain these active compounds are distinguished primarily by the fact that they can be used, for example, to save labor in particular in the breeding and production of hybrid seeds.
• the generative growth of a whole series of mono- and dicotyledonous plants can be controlled with the benzoylaminooxyacetic acid derivatives of the formula I or with agrochemicals which contain these compounds as an active ingredient, the vegetative growth being positively influenced for the crops in wide concentration ranges.
• the influence on generative plant growth is noticeable differently, depending on the plant culture.
• One of the main ways of controlling generative growth is based on the special properties of the benzoylaminooxyacetic acid derivatives described here, in various crop plants, in particular when used in monocotyledons, such as wheat, rye, barley, oats, rice, maize, sorghum, millet, forage grass, etc. but complement. in other plowing a, like sunflower or cotton a gametocidal effect to unfold. This leads to male sterility of the plant without noticeably affecting the fertility of the female flower parts. In numerous crop plants, an increase in flowering and / or the formation of parthenocarpic fruits (eg in tomatoes) can be observed at the same time.
• Male sterility is manifested either in a current male sterility, namely in that the male parts of the flower are not formed at all or in that the pollen is sterile, or it is shown in a functional male sterility in which the male parts of the flower are still formed but are unable to fertilize.
• the active compounds of the formula I can therefore also cause protogyny, that is to say that female flower parts capable of fertilization are formed prematurely or the growth of the male flower parts is delayed in such a way that cross-pollination can be carried out with selected bee pollen.
• Hybrid- Seed plays an important role in the main food crops and ornamental plants. Hybrids are usually more vital than pure species and deliver higher yields than the most productive parent variety.
• hybridization the breeder crosses two or more carefully selected inbred lines in an experimentally determined scheme and in this way obtains hybrid seeds, the plants of which have increased vigor and performance.
• Hybridization can also be carried out in a conventional manner in the case of the single-house synocratic maize plants, since male and female parts of flowers are formed at different points on the plant (diclinic flowers).
• the anthers that supply pollen form the tip of the maize plant, while the piston-shaped, female inflorescence is formed with the scar threads below the center of the plant.
• alternating rows of maize plants of the varieties or homozygous lines AA and BB are usually planted.
• the AA plants are disentangled in good time before the full development of the male inflorescences manually or mechanically and then dusted with pollen of a BB maize variety, with one on the AA plants AB hybrids (F 1 ).
• the process required for this is not only time-consuming and time-consuming, but inevitably leads to an injury to the plant and, particularly in the case of machine defembling, to an undesirable yield depression in the line / variety serving as the female parent (seed carrier).
• Another hybridization method is practiced for some cereals such as wheat, barley, millet and maize and for dicotyledons. This procedure is based on cytoplasmic, male-sterile plants and cross-pollination is carried out. These cytoplasmic sterile plants are limited to mother lines that have the same cytoplasm. As a result, cytoplasmic inherited weaknesses or errors, e.g. inadequate resistance to a particular pathogen or sensitivity to frost and the like, inevitably transferred to all hybrids originating from this mother line in this method. In addition, hybridization with cytoplasmic, male-sterile lines, particularly in the case of small-grain strawberries, but also in dicotyledon crops, requires complex measures of increased difficulty.
• breeding hybrid seeds always requires the production of male sterile and female intact plants.
• chemical sterilizing agents (gametoids) offers a simple, practicable and economical solution for the production of selective male sterility.
• Benzoylaminooxyacetic acid derivatives of the formula I show very good male gametocides Properties and are therefore suitable for this and related purposes. Their use in crops does not even let most of the problems associated with conventional hybridization methods appear.
• Both parent plants, which are to be crossed, are used in e.g. planted alternating rows.
• the line selected as a seed carrier or mother plant is treated with one of the active compounds of the formula I at the beginning of the flower formation, but before the male flower parts are formed. In this way, a number of male-sterile but fertile female parent plants are obtained.
• the other row remains untreated and serves as a pollen donor.
• Their male parts of the flower reach full training and supply the pollen for pollination of the mother plant or the seed carrier.
• the seeds produced by the mother plant are the hybrid seeds and can be harvested in a conventional manner. The grains of the male parent plants are harvested separately and used for other purposes.
• the active compounds of the formula I bring about further growth-regulating effects, for example a temporal control of the flower formation and subsequently controlled seed or fruit ripening.
• This type of flower stimulation is of particular economic interest for those plant varieties that bloom and bear fruit at the same time.
• the treatment of avocado or cotton plants with compounds of the formula I could on the one hand lead to an advantageous increase in the number of Inflorescences lead, on the other hand, the flowering and ripening process are subjected to a controlled rhythm. In this way, not only an increase in yield could be achieved, but also a more rational design of the harvest and thus cheaper marketing.
• This type of flowering stimulation also plays a crucial role in fruit production.
• This alternation is the result of a mismatch between the growth of the shoots and the flowering plant, in that the nutrition of the fruit curtain claims too many assimilates at the expense of the formation of flower buds.
• the conventional measures to improve fruit quality consist in a time-consuming mechanical thinning of very young fruits and in a growth-regulating cut of the so-called wild shoots; however, this inevitably leads to tree damage and low yields.
• benzoylaminooxyacetic acid derivatives of the formula I By using benzoylaminooxyacetic acid derivatives of the formula I, the growth of shoots can largely be suppressed in favor of generative growth, so that the vigorous growth contributes more to the flowering and fruiting. In this way, not only the fruit quality but also the yield can be improved and a phase shift in the alternance can be generated.
• the application of compounds of the formula I results in a significant increase in the flowering period, which can increase the possibility of pollination of all flowers.
• a prolongation of the flowering phase is also desirable for a large number of ornamental plants, especially flowers.
• the present invention thus also relates to the use of benzoylaminooxyacetic acid derivatives of the formula I or of compositions which contain these compounds as active substances for controlling plant growth, in particular for producing sterility in the male parts of flowers (use as gametocides) and / or for promoting the female parts of flowers and all resulting secondary effects, such as Yield increase, prolongation of flowering, increased flower formation, control of fruit formation or the ripening process and the like.
• the present invention also includes the production of agrochemicals, which is characterized by the intimate mixing of the active substance with one or more substances or groups of substances described herein. Also included is a method for the treatment of plants which is characterized by the application of the compounds of the formula I or the new agents.
• the application rates depend on the desired growth-regulating effect and should advantageously, depending on the development stage and plant species, i.e. depending on the time of application, can be determined experimentally.
• beneficial doses are at 0.5 to 4 kg ai / ha, application being necessary before the start of flowering, especially before the start of bud formation.
• split application is indicated, i.e. the application is preferably repeated periodically with smaller application rates.
• the application rates also depend on the type of application and are preferably between 2 to 6 kg AS / ha for simple leaf application, between 2 to 4 kg AS / ha for split: application and for soil (drench) application 3 to 12 kg AS / ha, depending on the soil type.
• Active ingredients of the formula I are usually used in the form of compositions and can be applied simultaneously or in succession to the area or plant to be treated with further active ingredients.
• These other active ingredients can be fertilizers, Trace element mediators or also selective herbicides, insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, together with any other carriers, surfactants or other application-promoting additives that are customary in formulation technology.
• Suitable carriers and additives can be solid or liquid and correspond to the substances useful in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, adhesives, thickeners, binders or fertilizers.
• a preferred method for applying an active ingredient of the formula I or an agrochemical composition which contains at least one of these active ingredients is application to the foliage (leaf application). If this procedure is carried out in good time at the beginning of flowering, a very selective male sterility can be created in this way.
• the active ingredients of formula I. can also get into the plant through the roots through the roots (systemic effect) by soaking the location of the plant with a liquid preparation or introducing the substances in solid form into the soil e.g. in the form of granules (soil application).
• other types of application are possible in special cases, e.g. the targeted treatment of plant stems or buds.
• the compounds of the formula I are used in unchanged form or, preferably, as agents together with the auxiliaries customary in formulation technology and are therefore used, for example, to form emulsion concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules, and also encapsulations in eg polymeric materials processed in a known manner.
• the application methods such as spraying, ver Misting, dusting, scattering or pouring are chosen according to the desired goals and the given conditions, just like the type of agent.
• the formulations i.e. the agents, preparations or compositions containing the active ingredient of formula I and optionally a solid or liquid additive are prepared in a known manner, e.g. by intimately mixing and / or grinding the active ingredients with extenders, e.g. with solvents, solid carriers, and optionally surface-active compounds (surfactants).
• extenders e.g. with solvents, solid carriers, and optionally surface-active compounds (surfactants).
• surfactants optionally surface-active compounds
• Possible solvents are: Aromatic hydrocarbons, preferably the fractions C s to C 12 ' such as xylene mixtures or substituted naphthalenes, phthalic acid esters such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as Ethanol, ethylene glycol, ethylene glycol monomethyl or ethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, and optionally epoxidized vegetable oils such as epoxidized coconut oil or soybean oil; or water.
• the addition of mineral oils or vegetable oils is particularly advantageous in formulations that are used in leaf application.
• Natural rock flours such as calcite, talc, kaolin, montmorillonite or attapulgite, are generally used as solid carriers, for example for dusts and dispersible powders.
• Silicic acid or highly disperse absorbent polymers can be added.
• Porous types such as pumice, broken brick, sepiolite or bentonite can be used as granular, adsorptive granulate carriers, and non-sorptive carrier materials, such as calcite or sand.
• a large number of pre-engineered materials of inorganic or organic nature such as, in particular, dolomite or comminuted plant residues can be used.
• suitable surface-active compounds are nonionic, cationic and / or anionic surfactants with good emulsifying, dispersing and wetting properties.
• surfactants are also to be understood as mixtures of surfactants.
• Suitable anionic surfactants can be both so-called water-soluble soaps and water-soluble synthetic surface-active compounds.
• soaps are the alkali, alkaline earth or optionally substituted ammonium salts of higher fatty acids (C 10 -C 22 ), such as the Na or K salts of oleic or stearic acid, or of natural fatty acid mixtures, for example from coconut or Tallow oil can be obtained.
• the fatty acid methyl taurine salts should also be mentioned.
• the fatty sulfonates or sulfates are generally in the form of alkali metal, alkaline earth metal or optionally substituted ammonium salts and have an alkyl radical with 8 to 22 carbon atoms, alkyl also includes the alkyl portion of acyl residues, for example the sodium or calcium salt of lignin sulfonic acid, dodecylsulfuric acid ester or a fatty alcohol sulfate mixture made from natural fatty acids. This subheading also includes the salts of sulfuric acid esters and sulfonic acids from fatty alcohol / ethylene oxide adducts.
• the sulfonated benzimidazole derivatives preferably contain 2-sulfonic acid groups and a fatty acid residue with 8-22 carbon atoms.
• Alkylarylsulfonates are, for example, the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or a naphthalenesulfonic acid / formaldehyde condensation product.
• Corresponding phosphates such as e.g. Salts of the phosphoric acid ester of a p-nonylphenol (4-14) ethylene oxide adduct or phospholipids in question.
• Suitable nonionic surfactants are primarily polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, which can contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the alkyl radical of the alkylphenols .
• nonionic surfactants are the water-soluble polyethylene oxide adducts containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups with polypropylene glycol, ethylene diaminopolypropylene glycol and alkyl polypropylene glycol with 1 to 10 carbon atoms in the alkyl chain.
• the compounds mentioned usually contain 1 to 5 ethylene glycol units per propylene glycol unit.
• nonionic surfactants are nonylphenol polyethoxyethanols, castor oil polyglycol ethers, polypropylene-polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and Octylphenoxypolyäthoxyäthanol mentioned.
• Fatty acid esters of polyoxyethylene sorbitan such as polyoxyethylene sorbitan trioleate, are also suitable.
• the cationic surfactants are primarily quaternary ammonium salts which contain at least one alkyl radical having 8 to 22 carbon atoms as N substituents and have low, optionally halogenated alkyl, benzyl or low hydroxyalkyl radicals as further substituents.
• the salts are preferably in the form of halides, methyl sulfates or ethyl sulfates, e.g. the stearyltrimethylammonium chloride or the benzyldi (2-chloroethyl) ethylammonium bromide.
• the use forms can be diluted down to 0.001% of active ingredient.
• Example HI Aminooxyacetic acid ethyl ester.
• Hydrogen chloride gas is introduced into a suspension of 200 g of aminooxyacetic acid hydrochloride in 900 ml of methanol until saturation.
• the reaction mixture is stirred at a temperature of 20-25 ° C for 24 hours.
• 700 ml of solvent are distilled off from the reaction solution.
• the residue is neutralized with potassium carbonate.
• This mixture is diluted with ether and filtered.
• the filtrate is evaporated and the oily residue is fractionated in vacuo. 136 g (70% of theory) of methyl aminooxyacetate are obtained as a yellow oil, b.p. 80 ° C./20 mb.
• Example H2 2,6-dichlorobenzoylaminooxyacetic acid methyl ester (compound no. 1.2).
• Example H3 2,6-dichlorobenzoylaminooxyacetic acid methyl ester (compound no. 1.2).
• Example H4 2,6-dichlorobenzoylaminooxyacetic acid methyl ester (compound no. 1.2).
• a suspension of 10.0 g of sodium hydride in 100 ml of tetrahydrofuran is mixed in portions with 41.0 g of N-hydroxy-2,6-dichlorobenzamide. After the evolution of gas has ceased, 33 g of methyl bromoacetate are added dropwise to this mixture at a temperature of 20-25 ° C. The reaction mixture is then heated to reflux for 2 hours. After the resulting precipitate has been separated off, the solution is washed with water and evaporated. By recrystallizing the residue from ethyl acetate, 30.0 g (54% of theory) of 2,6-dichlorobenzoylaminooxyacetic acid methyl ester are obtained.
• Example H6 2,6-dichlorobenzoylaminooxyacetic acid (compound no. 1.1).
• Example H7 N-methyl-2,6-dichlorobenzoylaminooxyacetic acid (compound no. 1.9).
• Example H8 2,6-dichlorobenzoylaminooxyacetic acid chloride (compound no. 1.11).
• Example H9 2,6-dichlorobenzoylaminooxyacetic acid amide (compound no. 1.10). Gaseous ammonia is passed into a solution of 2.8 g of 2,6-dichlorobenzoylaminooxyacetic acid chloride in 100 ml of ether until saturated. The mixture is then washed with water, dried and evaporated. The residue is recrystallized from ethyl acetate. This gives 0.7 g (25% of theory) of 2,6-dichlorobenzoylaminooxyacetic acid amide, mp. 168-171 ° C.
• Example H10 2,6-dichlorobenzoylaminooxyacetic acid-2,6-dichlorophenyl ester (compound no. 1.5).
• Example H12 N-methyl-2,6-dichlorobenzoylaminooxyacetic acid tert. butyl ester (Verb 1.7).
• a suspension of 1.3 g of sodium hydride in 200 ml of tetrahydrofuran is mixed in portions with 6.6 g of N-hydroxy-N-methyl-2,6-dichlorobenzamide. After the evolution of gas has ceased, 6.4 g of bromoacetic acid tert are added to this mixture at a temperature of 25-30 ° C. add dropwise butyl ester. The reaction mixture is then heated to reflux for one hour. After the resulting precipitate has been separated off, the solution is washed with water and evaporated.
• Emulsions of any desired concentration can be prepared from such concentrates by dilution with water.
• the solutions are suitable for use in the form of tiny drops.
• the active ingredient is dissolved in methylene chloride, sprayed onto the carrier and the solvent is then evaporated off in vacuo.
• Ready-to-use dusts are obtained by intimately mixing the carrier substances with the active ingredient.
• the active ingredient is mixed well with the additives and ground well in a suitable mill.
• Spray powder is obtained which can be diluted with water to form suspensions of any desired concentration.
• Example F 6 Emulsion concentrate
• Emulsions of any desired concentration can be prepared from this concentrate by dilution with water.
• Ready-to-use dusts are obtained by mixing the active ingredient with the carrier and grinding it in a suitable mill.
• the active ingredient is mixed with the additives, ground and moistened with water. This mixture is extruded and then dried in an air stream.
• the finely ground active ingredient is applied evenly in a mixer to the kaolin moistened with polyethylene glycol. In this way, dust-free coating granules are obtained.
• Example F 10 Suspension concentrate
• the finely ground active ingredient is intimately mixed with the additives. This gives a suspension concentrate from which suspensions of any desired concentration can be prepared by dilution with water.
• Formulation additives that increase the adhesion of the active ingredient to the plant e.g. mineral or vegetable oils, have a very beneficial effect on leaf application.
• Example B 1 Gametocidal activity in small-grain crops
• Wheat plants are grown at the start of flowering, i.e. sprayed evenly at about the 51/2 leaf stage with a spray mixture (3000 ppm active substance) made from wettable powder of the active ingredient. 2 to 4 weeks after application, but before pushing the anther, each ear is protected against cross-pollination by covering. The gametocidal effect is assessed at the time of harvest by counting the grains formed per ear. Untreated wheat plants serve as a comparison.
• a control group of wheat plants is treated, covered or isolated as in a) and cross-pollinated with pollen from another wheat variety.
• the fertilization ability is assessed at the time of harvest by counting the hybrid grains formed per ear. Untreated wheat plants and treated but covered plants serve as a comparison.
• the second control group treated with the compounds mentioned (test b) develops after cross-pollination like the untreated plants. The number of hybrid grains harvested is 85 to 100%. In the wheat plants treated with one of the compounds Nos. 1.1, 1.2, 1.3 and 1.4, the number of hybrid grains is even higher than in the untreated control group.
• Example B 2 Gametocidal activity in maize
• a control group of maize plants is treated as under a) and its male and female flower parts are carefully covered. Approx. 3 weeks after application, the flasks of the treated plants are cross-pollinated with bee pollen from another, selected type of corn. At harvest time, fertility is assessed by counting the hybrid kernels per flask. Untreated corn is used as a comparison.
• “Hark” soybeans are sown in plastic containers with a 6: 3: 1 soil-peat-sand mixture and placed in a climatic chamber. Through optimal temperature selection, lighting, adding fertilizer and irrigation, the plants develop after about 5 weeks until the 5-6 trifolia leaf stage. At this point, the plants are sprayed with the aqueous broth of an active ingredient of the formula I until thoroughly wetted.
• the drug concentrations are 10, 50, 100 and 500 ppm. The evaluation takes about 5 weeks after application of the active ingredient.

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• 1984
  • 1984-06-21 EP EP84810304A patent/EP0133155A3/fr not_active Withdrawn
  • 1984-06-25 IL IL72217A patent/IL72217A0/xx unknown
  • 1984-06-26 ZA ZA844859A patent/ZA844859B/xx unknown
  • 1984-06-27 JP JP59132842A patent/JPS6023349A/ja active Pending

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